Construction of Enantioselective Photochromic System Controlled by Chirality of the Reaction-Field

反应场手性控制的对映选择性光致变色体系的构建

• 批准号: 14540503
• 负责人: YOKOYAMA Yayoi
• 金额: $ 2.3万
• 依托单位: Tokyo Kasei Gakuin University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540503/
• 关键词: DNA; Photochromism; Diarylethene; Spiropyran; Film; Intercalation; Amino Anthoracene; Quaternary Ammonium Ion Complex; 第四級アンモニウム塩; 蛍光; フォトクロミック反応; 光環化反応; フォトクトミズム; 複合材料; 偏光吸収スペクトル; 吸光度; 旋光度

DNA- quaternary ammonium ion complex(DNA-QAIC) was obtained by the addition of dimethyldioctadecylammoniun salt to DNA, according to the procedures previously reported. We have clarified that DNA-QAIC can be the transparent matrices of photochromic reactions.The stretched films of DNA-quaternary ammonium ion complex (DNA-QAIC) incorporating diarylethene exhibited large reversible change in optical rotation by its photochromic reactions.Diarylethenes show similar conversion ratio to their colored form in solution, regardless of the presence or absence of the hydroxyl groups in their structure. The diarylethenes showed lower reactivity in DNA-QAIC film or in organic solvents like chloroform in the presence of DNA-QAIC, than in solution without DNA-QAIC. The diarylethene with hydroxyl groups at 2-positions of the benzothiophene rings, that is 1,2-bis(2-hydroxymethyl-3-benzothienyl)hexafluorocyclopentene, showed no coloration when it is dissolved in chloroform together with DNA-QAIC. It is … More because the conformation of the diarylethene was fixed to a non-cyclizable parallel conformation. It was suggested that the diarylethene molecules were partly intercalated between the DNA base pairs.It is well-known that amioanthracene can intercalate between DNA base pairs. The diarylethene with an aminoanthracene intercalated at the anthracene moiety between the DNA base pairs in solution. As the result, fluorescence property changed to some extent, although the photochromic reaction was observed.Although the photochromic reaction were not detected for the powder of spiropyran, the powder of DNA-QAIC incorporating spiropyran showed thermally reversible photochrimism. In this case, the spiropyran in the powder were considered to be intercalating into the DNA-QAIC, and DNA-QAIC can be the transparent matrices of photochromic reactions. The thermal decoloration reactions of spiropyrans in DNA-QAIC films was slower, and the absorbance at the photo-thermo-stationary state was smaller than those in polystyrene films. The structure and the motion of spiropyrans doped in the DNA-QAIC films were restricted, so that it was difficult to change to the corresponding merocyanine form. Less

DNA-季铵离子络合物(DNA-QAIC)是通过在DNA中加入二甲基二十八烷基铵盐而得到的。DNA-QAIC可以作为光致变色反应的透明基质，DNA-季铵离子络合物(DNA-QAIC)与二芳基乙烯形成的拉伸膜在光致变色反应中表现出较大的可逆旋光变化，二芳基乙烯的转化率与其在溶液中的有色形式相似，无论其结构中是否含有羟基。二芳基乙烯在DNA-QAIC膜或含DNA-QAIC的氯仿等有机溶剂中的反应活性低于在不含DNA-QAIC的溶液中的反应活性。苯并噻吩环上2位羟基的二芳基乙烯，即1，2-bis(2-hydroxymethyl-3-benzothienyl)hexafluorocyclopentene，，与DNAQAIC一起溶解在氯仿中时，没有显色。这是…更多的是因为二芳基乙烯的构象被固定为不可环化的平行构象。这表明二芳基乙烯分子部分插入了DNA碱基对之间。众所周知，氨基菲可以插入DNA碱基对之间。在溶液中，二芳基乙烯与氨基并茂插入到脱氧核糖核酸碱基对之间的蒽基团上。结果表明，虽然螺吡喃粉末未检测到光致变色反应，但荧光性质发生了一定程度的变化，但含有螺吡喃的DNA-QAIC粉末表现出热可逆的光致变色现象。在这种情况下，粉末中的螺吡喃被认为是插入到DNA-QAIC中，DNA-QAIC可以作为光致变色反应的透明基质。螺吡喃在DNA-QAIC膜中的热脱色反应较慢，在光热稳定状态下的吸光度小于聚苯乙烯膜中的吸光度。掺杂在DNA-QAIC薄膜中的螺吡喃的结构和运动受到限制，很难转变为相应的花菁形式。较少

项目成果

Masako Saito: "Reversible Change in Optical Rotation by Photochromism of Diarvlethenes in the Stretched DNA-Quaternary Ammonium Ion"Chemistry Letters. 32・9. 806-807 (2003)

Masako Saito：“拉伸 DNA-季铵离子中二乙烯基烯的光致变色导致的旋光的可逆变化”《化学快报》32・9（2003 年）。

Sujen Man Shrestha: "Synthessis of Novel Thermally Irreversible Photochromic 1-Aryl-1,3-butadiene Derivatives"Bulletin of the Chemical Society of Japan. 76(2). 363-367 (2003)

Sujen Man Shrestha：“新型热不可逆光致变色1-芳基-1,3-丁二烯衍生物的合成”日本化学会通报。

Masako Saito: "Preparation and Photochromic Properties of Powder and Films of DNA-Dodecyltrimethylammonium Ion Complex Containing Spiropyran Derivatives"Bulletin of the Chemical Society of Japan. 76・12. 2423-2429 (2003)

Masako Saito：“含有螺吡喃衍生物的DNA-十二烷基三甲基铵离子络合物的制备和光致变色性能”日本化学会通报76・12（2003）。

Preparation and Photochromic Properties of Powder and Films of DNA–Dodecyltrimethylammonium Ion Complex Containing Spiropyran Derivatives

• DOI: 10.1246/bcsj.76.2423
• 发表时间: 2003-12
• 期刊: Bulletin of the Chemical Society of Japan
• 影响因子: 4
• 作者: M. Saitō;K. Musha;Y. Yokoyama;Y. Yokoyama

Synthesis of Novel Thermally Reversible Photochromic Spiro[adamantine-2,7'(6'H)-benzothiophene].

新型热可逆光致变色螺[金刚烷-2,7(6H)-苯并噻吩]的合成。

• 发表时间: 2003
• 期刊: Bull.Chem.Soc.Jpn. 76(2)
• 作者: Yasushi Yokoyama;Mahmut Kose;Yasushi Yokoyama;Mahmut Kose;Mahmut Kose;Yasushi Yokoyama;Sujen Man Shrestha;Yasushi Yokoyama;Masako Saito;斉藤 雅子;Masako Saito;Yasushi Yokoyama
• 通讯作者: Yasushi Yokoyama